10-phenyl-benzanthrone and derivatives of the same



Patented May 2 1, 1929.

UNITED STATES PATENT OFFICE.

ROBERT BERLINER, BERTHOLD STEIN, AND WILLY TRAUTNER, OF ELBERFELD, GER-MANY, ASSIGNOBS '10 GRASSELIFI DYESTUFF CORPORATION, OF NEW YORK, N. Y.,

A CORPORATION OF DELAWARE.

IO-P HENYL-BENZANTHRONE AND DERIVATIVES OF THE SAME.

No Drawing. Application filed September 16, 1926, Serial No. 135,986,and in Germany October 20, 1925.

We'have shown in our co-pending application, Serial No. 135,989 filed oneven date that an intramolecular condensation takes place whencinnamylidene-anthrone compounds are heated to temperatures of about 250(3., .the condensation products being l-phenylbenzanthrones, i

We have now found that by treating these l-phenyl-benzanthrones withanhydrous aluminium chloride new compounds are formed. Analysis showsthese novel compounds to be isomeric with the l-phenyl-benzanthronecompounds. They differ from the latter however in their color and otherchemical reac tions as well as their melting points; the most remarkabledifference is in'the behavior of the two types of compounds with causticalkali. As we have described and claimed in our co-pending application,Serial No. 135. 987 filed on even date, alkali melt of the novelphenyl-benzanthrone produces a green Vat dyestuff, whereas alkali meltof the l-phenylbenzanthrone does not produce such a Vat dyestufi.

Elementary analysis shows that our novel benzanthrone compounds have thesame composition as the parent material. By the action of the anhydrousaluminum chloride a migration of the phenyl group is effected.

The new compounds are Bz-phenylbenzanthrpnes corresponding to. theprobable formu a:

. usually yellow colored well crystallized substances and are soluble toa certain extent in many organic solvents.

This molecular rearrangement takes place readily when heating thel-phenyl-benzanthronecompounds to temperatures of' above 100 0.;mixtures of anhydrous aluminium chloride and alkali metal chlorides areparticularly suited for promoting this reaction, but otheracidcondensing agents will similarly induce this reaction.

It is not necessary to start from isolated l-phenyl-benzanthronecompounds. The melts as obtained when heating cinnamylidene anthrones totemperatures of about 250 C. and containing the l-phenyl-benzanthronecompounds, can be reacted upon directly with an acid condensing agent,the molecular rearrangement takes place and our novel, isomericphenyl-benzanthrone compounds are likewise obtained.

The following examples will further illustrate our invention, the partsbeing byweight.

Example 1.'-A mixture of 4 parts anhydrous aluminium chloride and 1 partsodium chloride are molten and at 120125 C. one

5 part l-phenyl-benzanthrone of the melting point 181 C. graduallyadded. After all has been introduced the melt is kept at the sametemperature for a little longer, it is then poured into water acidifiedWithhydro chloric acid and well boiled up. The precipi-.

of the probable formula:

. do I 4 g i I: 40 Example 2.-'-1 part cinnamylidene-anthrone is heatedto 260 C. until formation of the l -phenyl-benzanthrone is oomplete,;themelt is allowed to cool to about 150 C. when ten mixture of 4 partsanhydrous aluminium chloride and 1- art sodium chloride kept at a temerature o HO-125 (3., the melt is kept at t is temperature for a littlewhile, then poured into water, acidified with hydro .chloric acid,boiled up, filtered off, the precipitate washed and dried. Aftercrystallization from glacial aceticacid yellow needles are obtainedwhich are identical with the 10- phenylrbenzanthrone of Example 1.,Example .3.+-3 parts l-phen' l-aIpha-hydroxy-benzanthrone containing tliin t e 4, 5 or 8 position are gradual added to a molten mixtureof-12parts anhydrous aluminium chloride and- 3 parts sono d1um chlorideheated, to 130,140' C. The melt is kept. at this temperature for alittle While, then poured into water, acidified with hydrochloric acid,boiled up and the precipitate isolated in the usual. manner, A yellow itis still liquid, it is then poured into a mol-- throne compound from themelt.

e hy drox ly solutions of the corresponding l-phenylben- -tiallyideritiba '130140 C. and kept at this temperature for a while, the meltis then poured into water 1 and the preci itate worked up as inExample 1. The cru e product is crystallized from pyridine. It isobtained as yellow crystals which dissolve in concentrated sulfurlc acidwith a red color, slightly different from the parent1-phenyl-beta-chlor-benzanthrone.

We claim: v 4 I 1. The process of "producing isomericphenyl-b'enzanthrone com ounds which consists in treatingI-phenylenzanthrone compounds with an acid condensing agent.

- 2." The process of producing isomeric 9o phenyl-benzanthronecom oundswhich consists in treating l-phenylenzanthrone compounds with anhydrousaluminium chloride.

3. The process of producing isomeric phenyl-benzanthrone compounds whichconsists in treating l-phenyl-benzanthrone compounds with a moltenmixture of anhydrous aluminium chloride and an alkali metal chloride attemperatures of between about 100 and 4. The process of producingisomeric phenyl-benzanthrone compounds which con- =s1sts in treatingwith anh drous aluminium' chloride the crude melt as o tained by heatingcinnamylidene-anthrone compounds to temperaturesof around 250 C. andcontaining 1- phen l-benzanthrone compounds.

5. he process of producing 10-phenylbenzanthrone which consists intreating 1- phenyl-benzanthrone at temperatures of about 120125 O. witha molten mixture of anhydrous aluminium chloride and sodium chlori e andisolating the 10'-phenyl-benzan- 6. As new products Bz-phenyl-benzan-'throne compounds which are isomeric with 1- phenyl-benzanthronecompounds, which are yellow colored crystalline substances, dis-.solving in concentrated sulfuric acid with colors different from thoseof thesulfuric acid zanthrone com ounds and which are substanwith'the"products obtained. when'treatin at temperatures of about 100-- 15 0 C.1-p enyl-benzanthrone compounds with anhydr usaluminium chloride.

7.- As a new product 10-phen l'-benzanthrone which is isomeric with l penyl-beu' 1.71am I 3 -zanthrone, which when crystallized from mixture ofanhydrous aluminium chloride lacial acetic acid forms yellow needles,meltand sodium chloride.

- mg at 199-200 (3., dissolving in concentrated In testimony whereof, weaflix our signa- 1 sulfuric acid with a yellowish-red color and ,tures.which is substantially identical with the prod- ROBERT BERLINER. notobtained by treating 1-phenyl-benzan- -BERTHOLD STEIN.

' throne at about 120-12Q C. with a molten 3 WILLY TRAUTNER.

